JP4181413B2 - Use of aromatic compounds as phase aligners and particle size reducers for quinacridone pigments - Google Patents

Abstract

The present invention relates to a process for producing alpha, gamma-I, gamma-II and gamma-III crystal modifications of quinacridone and transparent quinacridone pigments including the solid solutions of various quinacridones, using a variety of tris-aryl-s-triazines, particularly resorcinol triazine derivatives, or aromatic- or heteraromatic-compounds having at least one hydroxyl or keto group bonded to the ring, as an additive, prior to or concurrently with the oxidation of corresponding dihydroquinacridone salts.

Description

  The present invention relates to various tris-aryl-s-triazines, in particular resorcinol triazine derivatives, or aromatic- or heteroaromatics having at least one hydroxyl or keto group bonded to the ring as additives in the synthesis of the pigment quinacridone. The present invention relates to a process for the production of transparent quinacridone pigments containing alpha, gamma-I, gamma-II and gamma-III crystalline species of quinacridone and various quinacridone solid solutions using group-compounds.

  Hydrogen peroxide oxidation of dihydroquinacridone, as described in US Pat. No. 5,840,901, is a new environmentally friendly method for producing quinacridone pigments. This production method, like other oxidation methods, has one drawback, mainly resulting in a large particle size crude product. Any improvement of this method to produce small particle size pigments is highly desirable, and it is thereby dry milling (US Pat. No. 2,402,167 and US Pat. No. 3,030,370). And acid drowining (US Pat. No. 3,326,918 and US Pat. No. 3,607,336) would eliminate the need for expensive and undesirable finishing steps.

  It is well known that unsubstituted quinacridones form different crystalline phases, such as gamma, including alpha, beta, and gamma-I, gamma-II and gamma-III polytypes, depending on the experimental conditions. Important quinacridones currently on the market are in the beta, gamma-I and gamma-II crystal forms. Gamma-I and gamma-III crystalline phases quinacridone can be produced either by recrystallization in a specific solvent or by a dry milling process.

  The use of derivatized pigments as additives in the production of pigment quinacridone is well known. Some of the known quinacridone derivatives are, for example, pyrazolylmethylquinacridone; phthalimidomethylquinacridone; quinacridonesulfonic acid; various salts of quinacridonesulfonic acid and many others. Some of these quinacridone derivatives have been used as pigment grain growth regulators, and some others have been used to improve rheology.

  A known method for producing the pigment quinacridone is the grinding of large particle size crude quinacridone in the presence of large amounts of inorganic salts (which need to be removed later), as described for example in US Pat. No. 5,084,100. It is. The pigment quinacridone can be obtained by a tandem premilling-solvent ripening method as described in US Pat. No. 5,281,269 and US Pat. No. 4,541,872.

  The aforementioned additives have been used during pigment production, for example, by grinding, solvent treatment, or post-solvent treatment steps to further improve the properties of the pigment. For example, US Pat. No. 5,084,100 discloses a method in which crude quinacridone is ground by a ball mill in the presence of aluminum sulfate and dibasic esters of various carboxylic acids. Another method for preparing the pigment quinacridone is described in U.S. Pat.No. 4,455,173, where the crude quinacridone pigment is pasted with acid or ground in a ball mill and then preferably in an organic liquid. Is ground in the presence of 2-phthalimidomethylquinacridone particle size growth inhibitor. Various pigment derivatives for processing pigments including quinacridone pigments are also described in US Pat. Nos. 3,386,843; 4,310,359 and 5,472,494.

  The addition of certain quinacridone derivatives in the preparation of quinacridone via the polyphosphate ring closure route is reported in US Pat. No. 5,368,641 and US Pat. No. 5,755,873, which are pigment quinacridones, particularly the pigment 2,9-dimethyl. A method for producing quinacridone is disclosed. The use of such pigment derivatives in the preparation of the pigment quinacridone by oxidation of dihydroquinacridone is reported in US Pat. Nos. 5,424,429, 5,457,203 and 5,840,901.

  The preparation and use of triazine UV absorbers is described in the patent literature. These additives are used for automotive painting, photographic applications, polymer film coating and ink jet printing. Automobile coatings are described in UK Patent Application Publication Nos. 2,317,174 and 2,317,893, and in US Pat. Nos. 5,354,794; 5,556,973; 5,681,955; 5,726,309 and 5,106,891. Photographic applications are disclosed in US Pat. No. 3,843,371. Polymer film coatings are described in US Pat. Nos. 4,619,956 and 4,740,542. Inkjet printing is disclosed in US Pat. No. 5,096,489. Tris-aryl-s-triazine is generally understood to mean a tri-aryl compound in which at least one aryl group has an ortho hydroxy group relative to the point of attachment to the triazine ring. Resorcinol derivatives for the purposes of this application are compounds that are substituted in the 2,4-position with a hydroxyl group on at least one phenyl ring of a tris-aryl-s-triazine compound. US Pat. No. 5,726,309 describes resorcinol numbering, which is incorporated herein by reference in its entirety.

  Accordingly, it was an object of the present invention to provide a process for preparing transparent quinacridone pigments containing quinacridone alpha, gamma-I, gamma-II and gamma-III crystal species and various quinacridone solid solutions.

  The above objective is surprisingly the formula (B):

A process for producing a quinacridone pigment or a solid solution thereof,
Corresponding formula (A):

[Wherein X and Y are independently one or two substituents selected from the group consisting of H, F, Cl, C ₁ -C ₄ alkyl and C ₁ -C ₄ alkoxy] Or a salt of a mixture of two or more of the 6,13-dihydroquinacridone of formula (A), which is free of pigment residues and oxidants, It has been solved by a process characterized by oxidation in the presence of an aromatic hydroxyl or keto group-containing compound.

  That is, the present invention uses a hydroxyl or keto group-containing aromatic and heteroaromatic compound, such as a resorcinol triazine compound, as an additive in the oxidation of dihydroquinacridone (eg, hydrogen peroxide oxidation). , Gamma-II and gamma-III quinacridone and other transparent quinacridones and methods for obtaining solid solutions thereof comprising various compositions of structure (B). This additive is used in an amount of 1 to 25% by weight, preferably 1 to 10%, based on the weight of dihydroquinacridone.

  Dihydroquinacridone and quinacridone to which the present invention is applicable are represented by the formulas (A) and (B):

[Wherein X and Y are independently one or two substituents selected from the group consisting of H, F, Cl, C ₁ -C ₄ alkyl and C ₁ -C ₄ alkoxy] It is a compound shown by these.

C ₁ -C ₄ alkyl represents methyl, ethyl, n- and i-propyl, n-butyl, sec-butyl, i-butyl and tert-butyl, preferably methyl. C ₁ -C ₄ Alkoxy represents methoxy, ethoxy, n- and i- propoxy, n- butoxy, sec- butoxy, i- butoxy and tert- butoxy, preferably methoxy.

  Preferably, positions 2 and 9 of quinacridone of formula (A) and (B) are substituted.

  The process is used for the production of unsubstituted quinacridone, 2,9-dichloroquinacridone, 2,9-difluoroquinacridone, 4,11-dichloroquinacridone, 2,9-dimethylquinacridone and 2,9-dimethoxyquinacridone, or quinacridone / 2,9-dichloroquinacridone, quinacridone / 4,11-dichloroquinacridone, quinacridone / 2,9-dimethylquinacridone, quinacridone / 2,9-dimethoxyquinacridone, 2,9-dichloroquinacridone / 2,9-dimethylquinacridone, 2, It is particularly useful for the preparation of 9-dichloroquinacridone / 2,9-dimethoxyquinacridone or 2,9-dimethylquinacridone / 2,9-dimethoxyquinacridone solid solution pigment.

  The present invention relates to quinacridone of formula (B) by oxidation of the corresponding salt of 6,13-dihydroquinacridone of formula (A) or a mixture of two or more 6,13-dihydroquinacridone of formula (A) A method for producing the solid solution, characterized in that it comprises an oxidation step in which 6,13-dihydroquinacridone salt is oxidized in the presence of a selected aromatic additive.

  The selected aromatic compound is added before or during the oxidation of dihydroquinacridone to the corresponding quinacridone. Examples of preferred aromatic additives include 4,6-bis-, such as Tinuvin® 400 (Ciba Specialty Chemicals Corp.) and Cyasorb® 1164 (Cytec Corporation). (2,4-dimethylphenyl) -2- (2,4-dihydroxyphenyl) -s-triazine, or a red shifted s-triazine as disclosed, for example, in US Pat. Nos. 5,556,973 and 5,354,794, or UV absorbers based on high molar quenching s-triazines as disclosed in copending application Ser. No. 09 / 383,163 (US Pat. No. 6,255,483).

  An example of an oxidative manufacturing process is described in US Pat. No. 5,840,901 (incorporated herein by reference). This 6,13-dihydroquinacridone salt is, for example, in a basic medium (eg a basic mixture of water and alcohol) at a temperature above 30 ° C. (preferably 40-60 ° C., and most preferably 50 ° C.). Prepared by stirring 6,13-dihydroquinacridone for 5 minutes to 2.5 hours (preferably 20 minutes to 1.5 hours) at the corresponding reflux temperature.

  This oxidation reaction is carried out in a reaction medium obtained by combining a slurry consisting essentially of 6,13-dihydroquinacridone, an aromatic additive, a base and a suitable liquid phase with an oxidizing agent. A suitable liquid phase is any liquid medium that promotes the oxidation reaction and does not react to any significant extent with the oxidant.

A common liquid phase comprises 20 to 750 parts (preferably 40 to 600 parts) of water and 50 to 750 parts (preferably 100 to 600 parts) of alcohol per 100 parts of 6,13-dihydroquinacridone. It is a mixture of alcohol and water (parts are parts by weight). This alcohol is advantageously a lower alcohol, for example a C ₁ -C ₃ alkanol, preferably methanol. The reaction medium is preferably substantially free of other organic solvents. However, organic solvents are acceptable even in the reaction medium as long as they do not impair the 6,13-dihydroquinacridone salt formation or oxidation reaction.

  Any base capable of forming a salt of 6,13-dihydroquinacridone is useful in the reaction medium. Preferably, the base is an alkali metal hydroxide, most preferably sodium hydroxide or potassium hydroxide. In some cases it is advantageous to use a mixture of sodium hydroxide and potassium hydroxide. The molar ratio of base to 6,13-dihydroquinacridone is typically 1 to 7 moles of base per mole of 6,13-dihydroquinacridone. Preferably, the reaction medium contains 2.2 to 5 moles of base per mole of 6,13-dihydroquinacridone.

  The formation of 6,13-dihydroquinacridone salt can be observed under an optical microscope by the formation of 6,13-dihydroquinacridone salt crystals. Depending on the reaction conditions, the type of base and / or the substituent of 6,13-dihydroquinacridone, the salt is generally in the form of needles, prisms, cubes or platelets.

  This oxidation reaction is preferably performed under an inert gas stream (eg, a nitrogen stream).

  In one oxidation process, the oxidation is carried out by using an aqueous solution of hydrogen peroxide as an oxidant and a slurry of 6,13-dihydroquinacridone in a basic mixture of aqueous alcohol and base for 5 minutes to 6 hours (preferably 30 Minutes to 3.5 hours) and then by maintaining the reaction medium at high temperature with stirring for a period of time to complete the oxidation and promote recrystallization of the pigment. The reaction medium is advantageously maintained after the addition of hydrogen peroxide at a temperature above 50 ° C. (preferably at the reflux temperature) for 5 minutes to 5 hours (preferably 30 minutes to 4 hours). The pigment is then isolated by filtration, alcohol followed by warm water washing and drying. Bases and alcohols can be easily regenerated from the filtrate.

  The aqueous solution of hydrogen peroxide generally comprises 1 to 50 weight percent, preferably 5 to 30 weight percent, and most preferably 10 to 25 weight percent hydrogen peroxide. In general, a slight excess of hydrogen peroxide is used. The molar ratio of hydrogen peroxide to 6,13-dihydroquinacridone is, for example, 1.1-5 moles (preferably 1.2-3.5 moles) of hydrogen peroxide per mole of 6,13-dihydroquinacridone. is there.

  The oxidation of 6,13-dihydroquinacridone salt to the corresponding quinacridone by hydrogen peroxide is visually followed by the color change of the reaction mixture.

  The presence of an accelerating amount of catalyst in the oxidation step increases the yield of quinacridone. Moreover, the presence of the catalyst under the oxidation conditions described above results in a quinacridone product that is substantially free of quinacridonequinone (eg, containing less than 2.5 weight percent quinacridonequinone). Small amounts of quinacridone quinone are acceptable even in the final product, as long as their presence does not substantially reduce the saturation of the final quinacridone pigment.

  Any compound capable of catalyzing the oxidation of 6,13-dihydroquinacridone under the present reaction conditions can be utilized as the catalyst. A particularly suitable catalyst for use in the process of the present invention is, for example, a quinone compound used for the air oxidation of 6,13-dihydroquinacridone to quinacridone. Such quinone catalysts are well known in the art. In particular, suitable catalysts are anthraquinone compounds, in particular anthraquinone, and anthraquinone sulfonic acid derivatives, such as anthraquinone-2,6-disulfonic acid, or preferably anthraquinone-2-sulfonic acid, or a salt thereof, in particular a sodium salt or Including potassium salts, especially anthraquinone-2-sulfonic acid, sodium salt or potassium salt. The quinone catalyst is in an amount effective to catalyze the oxidation reaction (eg, 0.005 to 0.1 times the weight of 6,13-dihydroquinacridone, and most preferably 0 to the weight of 6,13-dihydroquinacridone. .01-0.05 times) in the reaction medium.

  Depending on the composition of the liquid phase, the recrystallization time and the temperature, transparent small particle size or opaque large particle size quinacridone pigments are formed. Low temperatures and short periods are advantageous for clear products, while high temperatures and long periods are advantageous for more opaque products.

  The different crystalline forms of the quinacridone product depend on the reaction conditions used, such as, for example, the type and concentration of base and the composition of the liquid phase and the type and concentration of particle growth inhibitors that may be present in the oxidation process. To generate. Further, the crystal seed of the quinacridone product is controlled by adding seed crystals of quinacridone pigment having about 1-10 percent of the target crystal seed. The seed crystals are preferably added before oxidation, most preferably before salt formation.

  The type of oxidation reaction is not limited to the hydrogen peroxide reaction described above. Dihydroquinacridone can alternatively be oxidized to the corresponding quinacridone using an aromatic nitro compound as an oxidizing agent in an alcoholic medium containing a base and a small amount of water. It is also known that dihydroquinacridone can be converted to the corresponding quinacridone by a process in which 6,13-dihydroquinacridone is oxidized with an oxygen-containing gas in a solvent and / or aqueous base system. Such a process is often referred to as “air oxidation” because air is conveniently used as the oxygen-containing gas. Furthermore, it is known that the oxidation of 6,13-dihydroquinacridone can be carried out by dissolving it in a polar solvent (eg DMSO) using air as the oxidant.

  One class of aromatic additives is generally understood to mean tris-aryl compounds, wherein at least one aryl group has an ortho hydroxy group relative to the point of attachment to the triazine ring. Where the resorcinol derivative for purposes of this application is substituted at the 2,4-position with a hydroxyl group on at least one phenyl ring of the tris-aryl-s-triazine compound. It is a compound.

  The tris-aryl-s-triazine is preferably of formula (I):

[Where:
k is 1 or 2; and when k = 1, G is hydrogen or —OR ₂₅ ;
E ₁ and E ₂ are, independently of one another, formula (Ia) or (Ib):

Wherein R ₂₅ is hydrogen; C ₁ -C ₁₈ alkyl; OH, halogen, —COOH, —COOR ₂₉ , —CONH ₂ , —CONHR ₃₀ , —CON (R ₃₀ ) (R ₃₁ ) ), —NH ₂ , NHR ₃₀ , —N (R ₃₀ ) (R ₃₁ ), —NHCOR ₃₂ , —CN, COR ₃₂ , —OCOR ₃₂ , phenoxy and / or C ₁ -C ₁₈ alkyl-, C ₁ -C -O- are interrupted, and C ₃ -C ₅₀ substituted by OH alkyl;; C ₃ -C ₆ alkenyl _C18 alkoxy - - or halo C ₁ -C ₁₈ alkyl which is substituted by substituted phenoxy ; glycidyl; C ₅ -C ₁₂ cycloalkyl; OH, C ₅ -C ₁₂ cycloalkyl substituted by C ₁ -C ₄ alkyl or -OCOR _32; which is unsubstituted or OH, Cl, C ₁ - C ₁₈ alkoxy Wakashi -COR ₃₂ or -SO ₂ -R _33;; or formula C ₇ -C ₁₁ phenylalkyl substituted by C ₁ -C ₁₈ alkyl:

Wherein T is hydrogen; C ₁ -C ₈ alkyl; C ₂ -C ₈ alkyl substituted by one or more hydroxyl groups or one or more acyloxy groups; oxyl; hydroxyl; -CH ₂ CN; C ₁ -C ₁₈ alkoxy; C ₅ -C ₁₂ cycloalkoxy; C ₃ -C ₆ alkenyl; C ₇ -C ₉ phenylalkyl; once by C ₁ -C ₄ alkyl phenyl ring, 2 times Or C ₇ -C ₉ phenylalkyl substituted three times; or aliphatic C ₁ -C ₈ alkanoyl;
R ₂₄ is hydrogen; C ₁ -C ₂₄ alkyl or C ₅ -C ₁₂ cycloalkyl; or 1 to 9 halogen atoms, OH, OR ₂₅ , halogen, —COOH, —COOR ₂₉ , —CONH ₂ , —CONHR ₃₀ , —CON (R ₃₀ ) (R ₃₁ ), —NH ₂ , NHR ₃₀ , —N (R ₃₀ ) (R ₃₁ ), —NHCOR ₃₂ , —CN, COR ₃₂ , —OCOR ₃₂ , —CN, —NO _{2, -SR 32, -SOR 32,} -SO 2 R 32, -P (O) (oR 25) 2, morpholinyl, piperidinyl, 2,2,6,6-tetramethyl piperidinyl, piperazinyl or N- methyl piperazinyl group which is unsubstituted or substituted by a combination thereof, C ₁ -C ₂₄ alkyl or C ₅ -C ₁₂ cycloalkyl; or 1-6 _{phenylene, -O -, - NR 29 -} , - CONR 29 - , -COO-, -OC _{-, - CH (R 33)} -, - C (R 33) 2 - or -CO- groups or combinations thereof are interrupted, or a C ₅ -C ₁₂ cycloalkyl or C ₁ -C ₂₄ alkyl; Or R ₂₄ is C ₂ -C ₂₄ alkenyl; halogen; —SR ₃₂ , SOR ₃₂ ; SO ₂ R ₃₂ ; —SO ₃ H; or SO ₃ M;
R ₂₆ , R ₂₇ and R ₂₈ are each independently H, C ₁ -C ₁₂ alkyl; C ₂ -C ₆ alkenyl; C ₁ -C ₁₈ alkoxy; C ₅ -C ₁₂ cycloalkoxy; C ₂ -C ₁₈ alkenoxy; halogen; -C≡N; C ₁ -C ₄ haloalkyl; C ₇ -C _{11 phenylalkyl; COOR 29; CONH 2; -CONHR} 30; -CON (R 30) (R 31); sulfo; C ₂ -C ₁₈ acylamino; OCOR _32; phenyloxy; or C ₁ -C ₁₈ alkyl, phenyloxy which is substituted by C ₁ -C ₁₈ alkoxy or halogen;
R ₂₉ is C ₁ -C ₁₈ alkyl; C ₃ -C ₁₈ alkenyl; C ₃ -C ₅₀ alkyl interrupted by O, NH, NR ₃₀ or S and / or substituted by OH; glycidyl; C ₅ -C ₁₂ cycloalkyl; C ₁ -C ₄ alkyl cyclohexyl; phenyl; C ₇ -C ₁₄ alkylphenyl; C ₆ -C ₁₅ bicycloalkyl; C ₆ -C ₁₅ bicycloalkenyl; C ₆ -C ₁₅ tricycloalkyl; C ₆ -C ₁₅ bicycloalkylalkyl; or C ₇ -C ₁₁ phenylalkyl;
R ₃₀ and R ₃₁ are, independently of one another, C ₁ -C ₁₂ alkyl; C ₃ -C ₁₂ alkoxyalkyl; C ₂ -C ₁₈ alkanoyl; C ₄ -C ₁₆ dialkylaminoalkyl or C ₅ -C ₁₂ cycloalkyl. Or R ₃₀ and R ₃₁ together are C ₃ -C ₉ alkylene or -oxaalkylene or -azaalkylene;
R ₃₂ is C ₁ -C ₁₈ alkyl; C ₁ -C ₁₂ alkoxy; C ₂ -C ₁₈ alkenyl; C ₇ -C ₁₁ phenylalkyl; C ₇ -C ₁₁ phenylalkoxy; C ₆ -C ₁₂ cycloalkyl; ₆ -C ₁₂ cycloalkoxy; or a phenoxy or phenyl; or -O- are interrupted, and be a good C ₃ -C ₅₀ alkyl optionally substituted by OH;
R ₃₃ is C ₁ -C ₁₈ alkyl; C ₂ -C ₁₈ alkenyl; C ₆ -C ₁₂ cycloalkyl; provided that at least one G is an —OR ₂₅ group;

When k = 2
E ₁ and E ₂ are groups of formula (Ia);
G is C ₂ -C ₁₆ alkylene, C ₄ -C ₁₂ alkenylene, xylylene, C ₃ -C ₂₀ alkylene interrupted by O and / or substituted by OH, or the formula: —CH ₂ CH (OH _{) CH 2 O-R 34 -OCH} 2 CH (OH) CH 2 -, - CO-R 35 -CO -, - CO-NH-R 36 -NH-CO -, - (CH 2) j -COO-G ₂₀ —OOC— (CH ₂ ) _j — (where j is a number in the range of 1 to 3) or the following formula:

Indicated by;
R ₃₄ is C ₂ -C ₁₀ alkylene; O, phenylene, or C ₄ -C ₅₀ alkylene interrupted by the group: -phenylene-E-phenylene-, where E is -O-, -S _{-, - SO 2 -, -} CH 2 -, - CO-, or -C (CH _{3) 2} - a is);
R ₃₅ is C ₂ -C ₁₀ alkylene, C ₂ -C ₁₀ oxaalkylene, C ₂ -C ₁₀ thiaalkylene, C ₆ -C ₁₂ arylene or C ₂ -C ₆ alkenylene;
R ₃₆ represents C ₂ -C ₁₀ alkylene, phenylene, tolylene, diphenylene methane or the following formula:

A group represented by:
M is an alkali metal].

  Alternatively, compounds of formula (I) are described as follows in the context of the present invention:

[Where:
G is hydrogen or —OR ₂₅ ;
k is 1,
E ₁ and E ₂ are, independently of one another, formula (Ia) or (Ib):

In a group represented, wherein R ₂₅ is hydrogen; C ₁ -C ₁₈ alkyl; OH, it is a C ₁ -C ₁₈ alkyl which is substituted by -COOR _29;
R ₂₄ is hydrogen; C ₁ -C ₂₄ alkyl or C ₅ -C ₁₂ cycloalkyl;
R ₂₆ , R ₂₇ and R ₂₈ are, independently of one another, hydrogen, C ₁ -C ₁₂ alkyl or C ₁ -C ₁₈ alkoxy;
R ₂₉ is C ₁ -C ₁₈ alkyl; provided that at least one G is an OR ₂₅ group.

  A halogen substituent is -F, -Cl, -Br or -I; preferably -F or -Cl, especially -Cl.

Alkylphenyl, phenyl substituted by alkyl; C ₇ -C ₁₄ alkylphenyl, for example, methylphenyl (tolyl), dimethylphenyl (xylyl), trimethylphenyl (mesityl), ethylphenyl, propylphenyl, butyl Including phenyl, dibutylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl.

  Glycidyl is 2,3-epoxypropyl.

  Alkyl where O, N or S are interrupted and unsubstituted or substituted by OH may generally contain one or more of the above heteroatoms in light of the scope of the proposed meaning. Where oxygen, nitrogen and sulfur atoms are not in close proximity. In general, heteroatoms and hydroxyls in an alkyl chain are not in close proximity; preferably the carbon atoms of the alkyl chain are bound to no more than one oxygen, nitrogen and sulfur atom.

C ₁ -C ₂₀ alkoxy are methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, iso-octyloxy, nonyloxy, undecyloxy, dodecyloxy, tetradecyloxy or pentadecyloxy, hexa Linear or branched radicals such as decyloxy, heptadecyloxy, octadecyloxy, nonadecyloxy or eicosyloxy.

Phenylalkyl is alkyl substituted with phenyl. C ₇ -C ₂₀ phenylalkyl is, for example, benzyl, α-methylbenzyl, α, α-dimethylbenzyl, phenylethyl, phenylpropyl, phenylbutyl, phenylpentyl, phenylhexyl, phenylheptyl, phenyloctyl, phenylnonyl, phenyl Including decyl, phenyldodecyl or phenyltetradecyl.

C ₄ -C ₁₂ cycloalkyl is, for example, cyclobutyl, cyclopentyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, in particular cyclohexyl.

Suitable examples of C ₄ -C ₁₂ cycloalkyl interrupted by one or more oxygen atoms are tetrahydrofuranyl, 1-oxa-4-cyclohexyl or 1,3-dioxa-4-cyclohexyl.

In the light of the indicated definition, alkenyl is, inter alia, vinyl, allyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methyl-but-2-enyl, n-oct-2-enyl, n-dodec-2-enyl, iso-dodecenyl, n-dodec-2-enyl, n-octadec-4-enyl. R _x , R ′ and R ″ as alkenyl are preferably C ₂ -C ₁₈ alkenyl, in particular vinyl or allyl, and R _y is preferably C ₃ -C ₁₈ alkenyl, in particular allyl.

C ₂ -C ₁₈ alkanoyl is, for example, acetyl, propionyl, acryloyl, methacryloyl or benzoyl.

C ₅ -C ₁₂ cycloalkenyl is, for example, 2-cyclopenten-1-yl, 2,4-cyclopentadien-1-yl, 2-cyclohexen-1-yl, 2-cyclohepten-1-yl or 2-cyclooctene. -1-yl.

C ₄ -C ₁₂ cycloalkoxy is, for example, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, cyclooctyloxy, cyclononyloxy, cyclodecyloxy, cycloundecyloxy, cyclododecyloxy, in particular cyclohexyl It is oxy.

Aryl is generally an aromatic hydrocarbon radical such as phenyl, biphenylyl or naphthyl. Aralkyl is generally alkyl substituted by aryl; thus C ₇ -C ₁₂ aralkyl includes, for example, benzyl, phenylethyl, phenylpropyl, phenylbutyl, phenylpentyl and phenylhexyl; benzyl and α-methyl Benzyl is preferred. Alkyl aryl, aryl substituted by alkyl; C ₇ -C ₁₈ alkylaryl, inter alia, methylphenyl (tolyl), dimethylphenyl (xylyl), trimethylphenyl, tetramethylphenyl, pentamethylphenyl, ethylphenyl Propylphenyl (eg cumyl), butylphenyl (eg tert-butylphenyl), methylbutylphenyl, dibutylphenyl, pentylphenyl, hexylphenyl, dihexylphenyl, heptylphenyl, octylphenyl, nonylphenyl, decylphenyl, undecyl Phenyl, dodecylphenyl, methyl naphthyl, dimethyl naphthyl, ethyl naphthyl, propyl naphthyl, butyl naphthyl, pentyl naphthyl, hexyl naphthyl, heptyl naphthyl Includes Okuchirunafuchiru; among these, particular importance, for example, tolyl, xylyl, propylphenyl phenyl and butylphenyl.

Particular examples of C ₆ -C ₁₂ aryl are phenyl, naphthyl and biphenylyl.

Heteroaryl -C ₃ -C ₁₂ aryl, pyridinyl, pyrimidinyl, triazinyl, pyrrolyl, furanyl, thiophenyl or quinolinyl.

R ₂₅ as unsubstituted or substituted C ₅ -C ₁₂ cycloalkyl is, for example, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl, methylcyclohexyl or acetyloxycyclohexyl; preferred are cyclohexyl and cyclododecyl is there.

  If the alkyl radical has a further component or if the individual radical is alkylene, the free valence and also the bond to the substituent may start from the same carbon atom or from different carbon atoms. . Preferably, the bond to the heteroatom starts from a different carbon atom.

Thus, R ₂₅ as substituted C ₁ -C ₁₂ alkyl is, for example, hydroxyalkyl, such as 2-hydroxyethyl, 3-hydroxypropyl or 2-hydroxypropyl; 2-hydroxy-3-methoxypropyl, 2-hydroxy- Alkoxyhydroxyalkyl, such as 3-ethoxypropyl, 2-hydroxy-3-butoxypropyl, 2-hydroxy-3-hexoxypropyl or 2-hydroxy-3- (2-ethylhexyloxy) -propyl; methoxycarbonylmethyl; Ethoxycarbonylmethyl, butoxycarbonylmethyl, octyloxycarbonylmethyl, 1-octyloxycarbonyl-1-methylmethyl, 1-octyloxycarbonyl-1-ethylmethyl or 1-octyloxycarbonyl-1-hexyl Alkoxycarbonylalkyl, such as methyl; or alkanoyloxyalkyl or alkenoyloxyalkyl, such as 2- (acetyloxy) ethyl, 2-acryloxyethyl or 2-methacryloxyethyl; or, for example, 3-acryloxy -Or 3-methacryloxy-2-hydroxypropyl.

R ₂₅ as alkyl substituted by OH, alkoxy, phenoxy, —COOR ₂₉ , and / or —OCOR ₃₂ , for example, has the following meaning: —CH ₂ CH (OH) CH ₂ O—R ₃₇ (where R ₃₇ may have one of the above definitions of alkyl, or may be, for example, phenyl, acetyl, propionyl, acryloyl or methacryloyl); or includes alkyloxycarbonylalkyl; examples of such radicals are _{, -CH 2 CH 2 OCOCH = CH} 2, -CH 2 CH (OH) C 8 H 17, -CH 2 CH (OH) C 12 H 25, -CH 2 CH (OH) CH 2 O-n-C 8 _{H 17, -CH 2 CH (OH} ) CH 2 O-C 6 H 5, -CH 2 CH (OH) CH 2 O-CH 2 CH (C 2 H 5) - (CH 2) 3 -CH 3, - OCH ₂ CH (OH) C _{2 OCOC (CH 3) = CH} 2, a _{-OCH 2 CH (OH) CH 2} OCOCH = CH 2.

Radical called acylamino or acyloxy, preferably each C ₂ -C ₁₂ acylamino or - acyloxy. Acyl is —CO—R, where R is an organic radical often containing 1 to 11 carbon atoms, generally C ₁ -C ₁₁ alkyl, C ₂ -C ₁₁ alkenyl, C ₆ -C ₁₀ aryl, C ₇ -C ₁₁ phenylalkyl or C ₇ -C ₁₁ alkylphenyl.

Compounds of formula (I) are known in most cases; examples of known compounds include the following:
2,4,6-tris (2,4-dihydroxyphenyl) -1,3,5-triazine, (compound (I))
2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, (compound (II))
2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, (compound (III))
2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, (compound (IV))
2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine,
2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine,
2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine,
2- (2-hydroxy-4-tridecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine,
2- [2-hydroxy-4- (2-hydroxy-3-butyloxypropyloxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine,
2- [2-hydroxy-4- (2-hydroxy-3-octyloxypropyloxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine,
2- [4- (dodecyloxy / tridecyloxy-2-hydroxypropoxy) -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine,
2- [2-hydroxy-4- (2-hydroxy-3-dodecyloxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine,
2- (2-hydroxy-4-hexyloxy) phenyl-4,6-diphenyl-1,3,5-triazine,
2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine,
2,4,6-tris [2-hydroxy-4- (3-butoxy-2-hydroxypropoxy) phenyl] -1,3,5-triazine,
2- (2-hydroxyphenyl) -4- (4-methoxyphenyl) -6-phenyl-1,3,5-triazine.

  Triazine UV absorbers are generally described in US Pat. Nos. 5,726,309; 5,681,955 and 5,556,973; British Patent Application Publication No. 2,317,714, PCT Application Publication No. 96/28431 and European Patent Application Publication No. 941989. Can be prepared by conventional synthetic methods. The preparation of compounds of formula (I) is described, for example, in European Patent Application Publication No. 434,608, PCT Application Publication No. 96-28,431 or a publication by H. Brunetti and CE Luethi, Helv. Chim. Acta 55, 1566 (1972). Or by analogy with the Friedel-Crafts reaction of halotriazines with the corresponding phenols.

Examples of selected resorcinol triazine compounds

  Other (hetero) aromatic hydroxyl-containing compounds can be selected from:

_{Wherein, R 37, R 38, R} 39 and R _40, independently of one another, hydrogen, OH, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, Cl, Br, F, COOH ; COOR 29 CN; CON (R ₃₀ ) ₂ ; N (R ₃₀ ) ₂ ; NO ₂ ]. A (hetero) aromatic wherein R ₃₇ , R ₃₈ , R ₃₉ and R ₄₀ are independently of one another hydrogen, OH, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, Cl, Br, F and COOH Group compounds are more preferred. Particularly preferred (hetero) aromatic compounds have, as illustrated in the examples, only one or two rings per molecule and at least one hydroxyl group bound to at least one such ring. Have. Aromatic and heteroaromatic compounds, as the term is used herein, include quinacridone sulfonic acid and its salts, phthalimidomethylquinacridone, imidazolylmethylquinacridone, pyrazolylmethylquinacridone, and diaryl diketopyrrolopyrrolesulfonic acid and its It does not include compounds containing pigment residues, such as salts.

  Particularly suitable aromatic compounds for the present invention comprise one or more aromatic rings having at least one hydroxyl group. The aromatic ring may be further substituted with an alkyl and / or carboxy group. Examples of aromatic compounds are phenols, cresols, thymols, disubstituted naphthols, phenanthrols, pyrocatechols, and bicyclic hydroxyl-containing compounds linked by alkylene, carbonyl, oxyl, and / or sulfonyl groups. Still other examples include resorcinol, hydroquinone, naphthol, phloroglucinol, dihydroxybenzoic acid, pyrogallol, naphthoquinone and dihydroxy-2-naphthoic acid.

  Another suitable classification of additives is the following formula (XII):

Wherein R ₄₀ and R ₄₁ are independently selected from hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, or halogen such as Cl, Br, or F. Naphthoquinones.

  The synthesis of crystalline phase specific quinacridone using non-pigment additives is a direct and efficient method, which is soluble in the alkaline medium used for the reaction and produced by simple washing at the end of the reaction Can be removed from the object. Depending on the additive selected of the present invention, the gamma-I, gamma-II or gamma-III crystalline phase of quinacridone can be prepared in exceptional yield. Various quinacridone solid solutions with high transparency can also be prepared using these additives in the peroxide oxidation process.

Therefore, the present invention also provides
a) Formula (A):

Wherein X and Y are independently of one another hydrogen, halogen, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy, and b) an effective amount of formula ( (I) to (XII) a (hetero) aromatic hydroxyl or keto group-containing compound and c) optionally an oxidant.

  Resorcinol triazine derivatives are effective ultraviolet (UV) absorbers. Since these products are not soluble in water, they can be incorporated into the pigment after oxidation by simple neutralization of the reaction mixture. This will further protect the pigment from photobleaching.

Therefore, yet another aspect of the present invention is
a) Formula (B):

[Wherein X and Y are independently one or two substituents selected from the group consisting of H, F, Cl, C ₁ -C ₄ alkyl and C ₁ -C ₄ alkoxy] B) a composition characterized in that it comprises an effective amount of a (hetero) aromatic hydroxyl-containing compound of formula (I), ie a quinacridone of formula (B) and ( It is a composition comprising a hetero) aromatic hydroxyl-containing compound.

  In general, an effective amount of the compound of formula (I) is from about 1 to about 20% by weight of the stabilizing composition, but this will vary depending on the particular substrate and application. An advantageous range is 1 to 5%, preferably 1.5 to 2.5%.

  The additive of the present invention can also be used in the oxidation of dihydroquinacridone using either sodium meta-nitrobenzenesulfonate or air as the oxidizing agent. The additive of the present invention is also used in the synthesis of quinacridone by cyclization of 2,5-dianilinoterephthalic acid in the presence of polyphosphoric acid, as described in US Pat. No. 3,257,405 and US Pat. No. 5,755,873. can do.

  Certain crystalline phases of quinacridone can be prepared, for example, by hydrogen peroxide oxidation of 6,13-dihydroquinacridone in the presence of resorcinol triazine derivative (I) to produce gamma-I phase quinacridone, Similar oxidation performed by the addition of catechol, resorcinol, hydroquinone and phloroglucinol not only produced gamma-I quinacridone, but also changed the particle size of the resulting pigment.

  US Pat. Nos. 4,197,404 and 5,457,203 report that the use of phthalimidomethylquinacridone derivatives for gamma phase specific oxidation of 6,13-dihydroquinacridone results in pigments with high tinting strength. However, if the same oxidation was performed with more than 1% phthalimidomethylquinacridone, the oxidation reaction did not complete. It is therefore very surprising that even at the 3-10% level, the aromatic additives described above have not reduced the conversion yield of the oxidation reaction. It was also unexpected that the above-described aromatic hydroxy compounds produced commercially useful pure polymorphic quinacridone in an exceptionally pleasing manner in an economically tasting manner.

  Hydrogen peroxide oxidation assisted by hydroquinone of 6,13-dihydroquinacridone produces gamma-I quinacridone, but surprisingly the combination of hydroquinone and pyrazolylmethylquinacridone produces gamma-II quinacridone. Even more surprising, oxidation of 6,13-dihydroquinacridone in the presence of 2-naphthol yields gamma-III quinacridone.

  Furthermore, the simultaneous oxidation of two or more dihydroquinacridones results in a very attractive solid solution corresponding to the composition used in the oxidation, which is why the oxidation procedure of the present invention is fairly common. Suggests that. The aromatic hydroxy compounds described above are believed to act as crystal size and / or phase aligners during the oxidation reaction, and washing at the end of the reaction leaves a pigment free of impurities. Consequently, another feature of the present invention is that the (hetero) aromatic hydroxyl or keto group of formulas (I)-(XII) as a phase director and / or particle size reducer. Use of containing compounds. This feature is also industrially important because in the end-use application of the pigment there is no confusion due to the incompatibility of these aromatic hydroxy compounds. Thus, various industrially useful quinacridone pigments can be produced in an environmentally friendly and economically tasting manner by using the additives of the present invention for their purposes.

  Transparent quinacridone or a solid solution of quinacridone can be prepared. For example, certain mixtures of 6,13-dihydroquinacridone and 2,9-dichloro-6,13-dihydroquinacridone have the corresponding composition by peroxide oxidation in the presence of resorcinol triazine derivative (I). A solid solution of quinacridone and 2,9-dichloroquinacridone is provided.

  When the aromatic (heteroaromatic) hydroxy compound of the present invention is added to dihydroquinacridone in a small amount of 3 to 10% by weight, or 3 to 5% by weight, the crystalline phase is gamma-I, gamma-II or gamma- Orientation to III or the formation of a solid solution of a specific composition results in significant differences in synthesis.

  In the absence of additives, the oxidation process produces beta quinacridone starting from 6,13-dihydroquinacridone. In the case of the oxidation of mixed dihydroquinacridone, with the aid of the additive of the present invention, highly desirable small particle size pigments with excellent color characteristics are produced.

  This process is particularly useful for the preparation of unsubstituted quinacridone, 2,9-dichloroquinacridone, 2,9-difluoroquinacridone, 4,11-dichloroquinacridone, 2,9-dimethylquinacridone and 2,9-dimethoxyquinacridone. . Furthermore, the production process is also suitable for the preparation of solid solutions comprising one or more quinacridone components. Thus, a feature of the present invention relates to this production method, wherein a mixture comprising two or more 6,13-dihydroquinacridones of “Formula (A)” is simultaneously oxidized by the production method of the present invention. Thus, a quinacridone solid solution product is obtained. The production method of the present invention includes quinacridone / 2,9-dichloroquinacridone, quinacridone / 4,11-dichloroquinacridone, quinacridone / 2,9-dimethylquinacridone, quinacridone / 2,9-dimethoxyquinacridone, 2,9-dichloroquinacridone / It is particularly practical for the preparation of 2,9-dimethylquinacridone, 2,9-dichloroquinacridone / 2,9-dimethoxyquinacridone or 2,9-dimethylquinacridone / 2,9-dimethoxyquinacridone solid solution pigments.

  Depending on the end use, it may be advantageous to add texture improvers and / or rheology improvers, for example by incorporation into an aqueous compacted mass, preferably prior to pigment isolation. Suitable texture improvers are in particular fatty acids of 18 or more carbon atoms, such as stearic acid or behenic acid, or amides or metal salts thereof, preferably calcium or magnesium salts, as well as plasticizers, waxes, abietic acid. A resin acid such as or a metal salt thereof, an aliphatic alcohol such as colophonium, alkylphenol or stearyl alcohol, or a vicinal diol such as dodecanediol-1,2, or a modified colophonium / maleic resin or fumaric acid / A colophonium resin or a polymer dispersant. The texture improver is preferably added in an amount of 0.1-30% by weight, most preferably 2-15% by weight, based on the final product.

  Suitable rheology improvers are, for example, the anti-aggregating agents mentioned above, and this is added in an amount of 2-10% by weight, most preferably 3-8% by weight, based on the final product.

  The quinacridone and quinacridone solid solution pigments of the present invention are suitable as colorants for inorganic or organic substrates. They are very suitable for coloring high molecular weight materials, and they can be processed into casts and molded articles or, for example, solvent or waterborne paints in automotive coatings Are used in ink and coating compositions. Preferred high molecular weight materials are plastics, which are then rolled, cast, molded or processed into fibers and industrial or automotive paint or ink paints.

  Suitable high molecular weight organic materials are, alone or as a mixture, thermoplastics, thermoset plastics or elastomers such as cellulose ethers; cellulose esters such as ethyl cellulose; linear or crosslinked polyurethanes; linear, crosslinked or unsaturated Polyesters; Polycarbonates; Polyolefins such as polyethylene, polypropylene, polybutylene or poly-4-methylpent-1-ene; Polystyrene; Polysulfones; Polyamides; Polycycloamides; Polyimides; Polyethers; Polyether ketones such as polyphenylene oxide; Poly-p-xylene; polyvinyl halides such as polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride or polytetrafluoroethylene; polyacrylates, polymethacrylates Acrylic and methacrylic polymers such as rate or polyacrylonitrile; rubbers; silicone polymers; phenol / formaldehyde resins; melamine / formaldehyde resins; urea / formaldehyde resins; epoxy resins; Includes rubber or chloroprene rubber.

  Generally, the pigment is used in an effective coloring amount of, for example, 0.01 to 30% by weight, preferably 0.1 to 10% by weight, based on the weight of the high molecular weight organic material to be colored. Therefore, the present invention also relates to a colored plastic composition characterized by comprising a plastic material and an effective coloring amount of pigment or pigment solid solution prepared by the production method of the present invention, and a method for producing the colored plastic composition. .

  The pigments of the present invention are easily dispersed and are immediately incorporated into an organic matrix to give a homogeneous color with high saturation and excellent light and weather resistance.

  The high molecular weight organic material is colored with the pigment of the invention by mixing the pigment into the substrate using a high shear method including a roll mill or mixing or grinding equipment, if desired in the form of a masterbatch. . The colored material is then brought to the desired final shape by known methods such as rolling, press molding, extrusion, brushing, casting or injection molding.

  The following examples further illustrate embodiments of the present invention. In these examples, all parts given are parts by weight unless otherwise stated. The x-ray diffraction pattern is measured with a RIGAKU GEIGERFLEX diffractometer D / Max II v BX.

Examples The following examples are for illustrative purposes only and should not be construed as limiting the invention in any way.

Example 1 (comparison)
6,13-dihydroquinacridone (36 g; 0.114 mol) was added to a 1 liter four-necked round bottom flask equipped with a reflux condenser, mechanical paddle blade stirrer, and thermocouple element, and dispersed in methanol (210 ml). . An aqueous solution of sodium hydroxide (45.8 g; 0.537 mol; 50%) was added slowly using a dropping funnel over 10 minutes and the viscous dispersion was stirred at 55 ° C. for 1 hour. To this was added sodium anthraquinone monosulfonate (0.5 g), and the mixture was heated to reflux. To the resulting mixture, an aqueous solution of hydrogen peroxide (34.0 ml; 0.175 mole; 16.9%) was added at a rate of 0.15 ml / min using a Brinkmann pump. After the addition, the reaction mixture was stirred at reflux for an additional 10 minutes and then water (100 ml) was added. The product was filtered, washed with water until pH 7.5-8.0, then dried in an air oven at 80 ° C. overnight to give 34.5 g of a dark brown powder. The product exhibited a β _1/2 value of 0.306 at 2θ 5.9, corresponding to beta-quinacridone (FIG. 1).

Example 2
6,13-dihydroquinacridone (36 g; 0.114 mol) was added to a 1 liter four-necked round bottom flask equipped with a reflux condenser, mechanical paddle blade stirrer, and thermocouple element, and dispersed in methanol (210 ml). . An aqueous solution of sodium hydroxide (45.8 g; 0.537 mol; 50%) was added slowly using a dropping funnel over 10 minutes and the viscous dispersion was stirred at 55 ° C. for 1 hour. To this, resorcinol triazine derivative (compound (1), 1.08 g, 3%) and sodium anthraquinone monosulfonate (0.5 g) were added, and the mixture was heated to reflux. To the resulting mixture, an aqueous solution of hydrogen peroxide (34.0 ml; 0.175 mole; 16.9%) was added at a rate of 0.15 ml / min using a Brinkmann pump. After the addition, the reaction mixture was stirred at reflux for an additional 10 minutes and then water (100 ml) was added. The product was filtered, washed with water until pH 7.5-8.0, then dried in an air oven at 80 ° C. overnight to give 32.2 g of red powder. This product exhibited a β _1/2 value of 0.312 at 2θ 6.5, corresponding to gamma-I-quinacridone (FIG. 2). This experiment demonstrated the gamma-I-orientation effect of compound (I).

Example 3
Example 2 was repeated, except that a higher concentration of compound (1) (3.6 g, 10% by weight relative to dihydroquinacridone) was added prior to the addition of hydrogen peroxide. The product exhibited a β _1/2 value of 0.354 at 2θ 6.6, corresponding to gamma-I-quinacridone (FIG. 3). This product showed higher clarity than the product of Example 2. This experiment demonstrated that Compound (I) acts not only as a gamma-I phase aligning agent but also as a particle size reducing agent.

Example 4 (comparison)
Prior to the addition of hydrogen peroxide, instead of compound (1), pyrazolylmethylquinacridone (1% by weight relative to dihydroquinacridone; 2.19 g in a paste form with a concentration of 16.43% in water) was added. Except that, Example 2 was repeated. This product (35.1 g) exhibited a β _1/2 value of 0.446 at 2θ 6.6, corresponding to gamma-III-quinacridone (FIG. 4).

Example 5
Prior to addition of hydrogen peroxide, instead of compound (1), compound (1) (1.08 g, 3% by weight with respect to dihydroquinacridone) and pyrazolylmethylquinacridone (1% by weight with respect to dihydroquinacridone; in water; Example 2 was repeated, except that a mixture of 2.19 g) was added in a paste form with a concentration of 16.43%. This product (35.4 g) exhibited a β _1/2 value of 0.398 at 2θ 6.5, corresponding to gamma-I-quinacridone (FIG. 5). This experiment demonstrated the gamma-I orientation effect of compound (I). This product showed higher clarity than the product of Example 2.

Example 6
Prior to addition of hydrogen peroxide, instead of compound (1), compound (1) (1.08 g, 3% by weight with respect to dihydroquinacridone) and phthalimidomethylquinacridone (0.36 g, 1 weight with respect to dihydroquinacridone) Example 2 was repeated, except that a mixture with%) was added. This product (35.1 g) exhibited a β _1/2 value of 0.398 at 2θ 6.5, corresponding to gamma-I-quinacridone (FIG. 6). This product showed higher clarity than the product of Example 2.

Example 7 (comparison)
6,13-dihydroquinacridone (35 g; 0.111 mol) was added to a 1 liter four-necked round bottom flask equipped with a reflux condenser, a mechanical paddle blade stirrer, and a thermocouple element, and dispersed in methanol (230 ml). . An aqueous solution of sodium hydroxide (53.5 g; 0.668 mol; 50%) was slowly added using a dropping funnel over 10 minutes and the viscous dispersion was stirred at 55 ° C. for 1 hour. To this was added phthalimidomethylquinacridone (1.2 g, 3.4%) and sodium anthraquinone monosulfonate (0.5 g), and the mixture was heated to reflux for 1 hour. To the resulting mixture, an aqueous solution of hydrogen peroxide (61 ml; 0.315 mol; 16.9%) was added using a peristaltic pump at a rate of 0.3 ml / min. After the addition, the reaction mixture was stirred at reflux for an additional 10 minutes and then water (100 ml) was added. The product was filtered, washed with water until pH 7.5-8.0, then dried in an air oven at 80 ° C. overnight to give 27.9 g of a red powder. This product exhibited a β _1/2 value of 0.511 at 2θ 6.22, corresponding to alpha-quinacridone (FIG. 7).

Example 8
Example 7 was repeated, except that compound (1) (1.1 g; 3.1 wt% with respect to dihydroquinacridone) was added along with dihydroquinacridone. The product (27.5 g) exhibited a β _1/2 value of 0.471 at 2θ 6.5, corresponding to gamma-I-quinacridone (FIG. 8).

Example 9
Example 7 was repeated except that instead of dihydroquinacridone, a mixture of 6,13-dihydroquinacridone (26 g) and 2,9-dichloro-6,13-dihydroquinacridone (11 g) was added. The product (29.2 g) exhibited a β _1/2 value of 0.520 at 2θ 6.0, corresponding to a quinacridone solid solution (FIG. 9).

Example 10
Compound (1) (1.1 g; 3.1 wt% with respect to dihydroquinacridone) was added together with a mixture of 6,13-dihydroquinacridone and 2,9-dichloro-6,13-dihydroquinacridone. Except that, Example 9 was repeated. The product (25.2 g) exhibited a β _1/2 value of 0.650 at 2θ 6.0, corresponding to a quinacridone solid solution (FIG. 10). This compound was more transparent than the product of Example 9, indicating that the particle size is smaller than that of Example 9.

Example 11 (comparison)
To a 1 liter four-necked round bottom flask equipped with a reflux condenser, mechanical paddle blade stirrer and thermocouple element was added 6,13-dihydroquinacridone (18 g; 0.057 mol) and 2,9-dichloro-6,13-. Dihydroquinacridone (27 g; 0.07 mol) was added and dispersed in methanol (230 ml). An aqueous solution of sodium hydroxide (53.5 g; 0.668 mol; 50%) was slowly added using a dropping funnel and the viscous dispersion was stirred at 55 ° C. for 1 hour. To this was added phthalimidomethylquinacridone (1.5 g, 3.3%) and sodium anthraquinone monosulfonate (0.5 g), and the mixture was heated to reflux. To the resulting mixture, an aqueous solution of hydrogen peroxide (74 ml; 0.384 mol; 16.9%) was added at a rate of 0.3 ml / min using a Brinkmann pump. After the addition, the reaction mixture was stirred at reflux for an additional 10 minutes and then water (100 ml) was added. The product was filtered, washed with water until pH 7.5-8.0, then dried in an air oven at 80 ° C. overnight to give 41.0 g of dark red powder (FIG. 11). ).

Example 12
Example 11 was repeated, except that compound (1) (1.5 g; 3.5 wt% relative to dihydroquinacridone) was added after the addition of phthalimidomethylquinacridone. This compound was more transparent than the product of Example 11 by rub-out, indicating that the particle size is small (FIG. 12).

Example 13
Example 2 was repeated, except that compound (2) (1.08 g; 3% by weight with respect to dihydroquinacridone) was added instead of compound (1) prior to hydrogen peroxide addition. The product (35 g) exhibited a β _1/2 value of 0.322 at 2θ 6.5, corresponding to gamma-III-quinacridone (FIG. 13).

Example 14 (comparison)
To a 1 liter four-necked round bottom flask equipped with a thermometer, stirrer and reflux condenser was added 6,13-dihydroquinacridone (36.0 g; 0.1145 mol) and methanol (207 ml). The mixture was stirred for 15 minutes at moderate speed to ensure a homogeneous slurry. Aqueous sodium hydroxide (45.8 g; 0.572 mol; 50%) was added to the slurry and the mixture was stirred at 55 ° C. for 1 hour. After the addition of sodium anthraquinone monosulfonate (0.45 g), the slurry was heated to reflux. To the resulting mixture, an aqueous solution of hydrogen peroxide (67.5 g; 16.85%) was added at a rate of 0.3 ml / min using a Cole-Parmer peristaltic pump. After the addition was complete, the reaction mixture was stirred for 15 minutes and then water (100 ml) was added. The product was filtered and washed with warm water until the pH of the filtrate was 8.5 or lower and the conductivity of the filtrate was 110% or lower of the conductivity of the washing water. The violet solid product (yield: 35.9 g; 99.72%) obtained after drying in an oven at 80 ° C. was ground. This product exhibited the X-ray diffraction pattern of betaquinacridone. The rubout data showed a brownish purple color masstone and a turbid shade, consistent with a large particle size beta quinacridone crude product.

Example 15
To a 1 liter four-necked round bottom flask equipped with a thermometer, stirrer and reflux condenser was 6,13-dihydroquinacridone (36.0 g; 0.1145 mol), catechol (1.08 g) and methanol (207 ml). added. The mixture was stirred for 15 minutes at moderate speed to ensure a homogeneous slurry. To this slurry was added aqueous sodium hydroxide (45.8 g; 50%) and the mixture was stirred at 55 ° C. for 1 hour. After the addition of sodium anthraquinone monosulfonate (0.45 g), the slurry was heated to reflux. To the resulting mixture, an aqueous solution of hydrogen peroxide (67.5 g; 16.85%) was added at a rate of 0.3 ml / min using a Cole Palmer peristaltic pump. After the addition was complete, the reaction mixture was stirred for 15 minutes and then water (100 ml) was added. The product was filtered and washed with warm water until the pH of the filtrate was 8.5 or lower and the conductivity of the filtrate was 110% or lower of the conductivity of the washing water. The red solid product (yield: 35.9 g; 99.72%) obtained after drying in an oven at 80 ° C. was ground. This product exhibited an X-ray diffraction pattern of gamma-I quinacridone. The love-out data showed a bluish red with a very attractive small particle size.

  Catechol promoted the reaction of quinacridone to the gamma-I crystalline species.

Example 16
Example 15 was repeated except that resorcinol (1.08 g) was used instead of catechol. The red solid product (yield: 35.9 g; 99.72%) obtained after drying in an 80 ° C. oven was ground. This product exhibited an X-ray diffraction pattern of gamma-I quinacridone. The labout data showed a semi-opaque red pigment.

  Resorcinol promoted the reaction of quinacridone to the gamma-I crystalline species.

Example 17
Example 15 was repeated except that hydroquinone (1.08 g) was used instead of catechol. The red solid product (yield: 35.9 g; 99.72%) obtained after drying in an 80 ° C. oven was ground. This product exhibited an X-ray diffraction pattern of gamma-I quinacridone. Love-out data showed an opaque yellowish red pigment.

  Hydroquinone promoted the reaction of quinacridone to the gamma-I crystalline species.

Example 18
Example 15 was repeated except that phloroglucinol (1.08 g) was used instead of catechol. The red solid product (yield: 35.9 g; 99.72%) obtained after drying in an 80 ° C. oven was ground. This product exhibited an X-ray diffraction pattern of gamma-I quinacridone. Love-out data showed an opaque yellowish red pigment.

  Phloroglucinol promoted the reaction of quinacridone to the gamma-I crystalline species.

Example 19
Example 15 was repeated except that 2-naphthol (1.08 g) was used instead of catechol. The dark red solid product (yield: 35.9 g; 99.72%) obtained after drying in an 80 ° C. oven was ground. This product showed an X-ray diffraction pattern of gamma-III quinacridone. The love-out data showed a very bluish red, very small particle size pigment.

  2-Naphthol directed the reaction to the gamma-III crystal seed of quinacridone.

Example 20
Example 15 was repeated except that 3,4-dihydroxybenzoic acid (1.08 g) was used instead of catechol. The red solid product (yield: 35.9 g; 99.72%) obtained after drying in an 80 ° C. oven was ground. This product exhibited an X-ray diffraction pattern of gamma-I quinacridone with a large particle size. Love-out data showed an opaque yellowish red pigment.

  3,4-Dihydroxybenzoic acid promoted the reaction of quinacridone to the gamma-I crystalline species.

Example 21
Example 15 was repeated except that pyrogallol (1.08 g) was used instead of catechol. The red solid product (yield: 35.9 g; 99.72%) obtained after drying in an 80 ° C. oven was ground. This product exhibited an X-ray diffraction pattern of gamma-I quinacridone. The love-out data showed a bluish red with a very attractive small particle size.

  Pyrogallol promoted the reaction of quinacridone to the gamma-I crystalline species.

Example 22
Example 15 was repeated except that 1,4-naphthoquinone (1.08 g) was used instead of catechol. The red solid product (yield: 35.9 g; 99.72%) obtained after drying in an 80 ° C. oven was ground. This product exhibited an X-ray diffraction pattern of gamma-I quinacridone. The love-out data showed a bluish red with a small particle size.

  1,4-Naphthoquinone promoted the reaction of quinacridone to the gamma-I crystalline species.

Example 23
Example 15 was repeated except that 1,4-dihydroxy-2-naphthoic acid (1.08 g) was used instead of catechol. The red solid product (yield: 35.9 g; 99.72%) obtained after drying in an 80 ° C. oven was ground. This product showed a very well resolved X-ray diffraction pattern of gamma-I quinacridone. The love-out data showed a semi-opaque yellow hue.

  1,4-Dihydroxy-2-naphthoic acid promoted the reaction of quinacridone to the gamma-I crystalline species.

Example 24
Into a 1 liter four-necked round bottom flask equipped with a thermometer, stirrer and reflux condenser, 2,9-dichloro-6,13-dihydroquinacridone (18.0 g; 0.047 mol), 6,13-dihydroquinacridone (27.0 g; 0.086 mol), catechol (1.08 g) and methanol (185 ml) were added. The mixture was stirred for 15 minutes at moderate speed to ensure a homogeneous slurry. To this slurry was added aqueous sodium hydroxide (64.2 g; 50%), and the mixture was stirred at reflux for 1 hour, and sodium anthraquinone monosulfonate (0.5 g) was added. To the resulting mixture, an aqueous solution of hydrogen peroxide (67.5 g; 16.85%) was added at a rate of 0.3 ml / min using a Cole Palmer peristaltic pump. After the addition was complete, the reaction mixture was stirred for 15 minutes and then water (100 ml) was added. The product was filtered and washed with warm water until the pH of the filtrate was 8.5 or lower and the conductivity of the filtrate was 110% or lower of the conductivity of the washing water. The magenta solid product (yield: 44.9 g; 99.78%) obtained after drying in an 80 ° C. oven was ground. This product showed an X-ray diffraction pattern of a binary solid compound of 2,9-dichloroquinacridone and unsubstituted quinacridone. The love-out data showed a bluish red pigment with a very attractive medium particle size.

  This pigment is a unique two-component solid compound in which both 2,9-dichloroquinacridone and unsubstituted quinacridone have reached their new crystal structure by releasing their individual uniqueness.

Example 25
To a 1 liter four-necked round bottom flask equipped with a thermometer, stirrer, inlet tube and condenser was added 2,9-dichloro-6,13-dihydroquinacridone (40.0 g; 0.1044 mol), 6,13. Dihydroquinacridone (5.0 g; 0.0159 mol), catechol (1.08 g) and methanol (280 ml) were added. The mixture was stirred for 15 minutes at moderate speed to ensure a homogeneous slurry. An aqueous potassium hydroxide solution (136.8 g; 45%) was added to the slurry, and the mixture was stirred for 1 hour while refluxing, and sodium anthraquinone monosulfonate (0.5 g) was added. To the resulting mixture, an aqueous solution of hydrogen peroxide (67.5 g; 16.85%) was added at a rate of 0.3 ml / min using a Cole Palmer peristaltic pump. After the addition was complete, the reaction mixture was stirred for 15 minutes and then water (100 ml) was added. The product was filtered and washed with warm water until the pH of the filtrate was 8.5 or lower and the conductivity of the filtrate was 110% or lower of the conductivity of the washing water. The magenta solid product (yield: 44.9 g; 99.78%) obtained after drying in an 80 ° C. oven was ground. This product showed an X-ray diffraction pattern of gamma phase 2,9-dichloroquinacridone. The love-out data showed a very attractive medium particle size magenta color pigment.

  Catechol promoted solid solution formation. This pigment is a Host-Guest solid solution of 2,9-dichloroquinacridone and unsubstituted quinacridone, where 2,9-dichloroquinacridone is the host with respect to unsubstituted quinacridone. work.

Example 26
To a 1 liter four-necked round bottom flask equipped with a thermometer, stirrer, and condenser was added 6,13-dihydroquinacridone (24.0 g; 0.0764 mol), 2,9-dichloro-6,13-dihydroquinacridone ( 16.0 g; 0.0418 mol), catechol (1.2 g) and methanol (202 ml) were added. The mixture was stirred for 15 minutes at moderate speed to ensure a homogeneous slurry. To this slurry, aqueous potassium hydroxide (159.4 g; 45%) was added while maintaining the temperature below 50 ° C. The slurry was stirred efficiently at 50-60 ° C. for 15 minutes. To this slurry was added sodium metanitrobenzoate (23.0 g) followed by water (26.0 ml). The reaction mixture was heated to reflux and maintained at reflux temperature for 3 hours. The reaction mixture was quenched with methanol (100 ml) followed by water (100 ml) and stirring was continued for 15 minutes. The slurry is filtered and washed with an aqueous methanol solution (50%), followed by hot water until the pH of the filtrate is 8.5 or less and the conductivity of the filtrate is 110% or less of the conductivity of the wash water. Washed with water. The bluish red solid product obtained (yield: 39.8 g; 99.5%) was dried in an 80 ° C. oven and ground. This product showed an X-ray diffraction pattern of a binary solid compound of 2,9-dichloroquinacridone and unsubstituted quinacridone. The love-out data showed a bluish red pigment with a very attractive medium particle size.

  This pigment is a unique two-component solid compound in which both 2,9-dichloroquinacridone and unsubstituted quinacridone have reached their new crystal structure by releasing their individual uniqueness.

Example 27
2,9-Dichloro-6,13-dihydroquinacridone (45.0 g; 0.117 mol) was added to a 1 liter four-necked round bottom flask equipped with a reflux condenser, mechanical paddle blade stirrer and thermocouple element, Disperse in methanol (280 ml). An aqueous solution of potassium hydroxide (137 g, 45%, 1.04 mol) was slowly added using a dropping funnel and the reaction mixture was stirred at 60 ° C. for 1 hour. Before the dispersion was heated to reflux, sodium anthraquinone monosulfonate (0.5 g, 0.2 mmol) was added. To the resulting mixture, an aqueous solution of hydrogen peroxide (74 ml; 16.9%; 0.384 mol) was added dropwise at a rate of 0.3 ml / min using a Brinkman pump. After the addition, the reaction mixture was stirred for an additional 10 minutes and then water (100 ml) was added. The product was filtered, washed with water (to pH 7.5-8.0) and then dried in an air oven at 80 ° C. overnight to give 43.1 g of dark magenta powder. This product showed an X-ray diffraction pattern of gamma phase 2,9-dichloroquinacridone (FIG. 14).

Example 28
Example 27 was repeated, except that compound (1) (1.5 g, 3.3% by weight relative to dichlorodihydroquinacridone) was added prior to the addition of hydrogen peroxide. This product (41.6 g) showed an X-ray diffraction pattern of alpha phase 2,9-dichloroquinacridone (FIG. 15).

Example 29 (comparison)
Example 27 was repeated, except that phthalimidomethylquinacridone (1.5 g, 3.3 wt% with respect to dichlorodihydroquinacridone) was added in place of compound (1) prior to hydrogen peroxide addition. This product (42.4 g) showed an X-ray diffraction pattern of gamma phase 2,9-dichloroquinacridone (FIG. 16).

Example 30
Before hydrogen peroxide addition, compound (1) (1.5 g, 3.3 wt% with respect to dichlorodihydroquinacridone) and phthalimidomethylquinacridone (1.5 g, 3.3 wt% with respect to dichlorodihydroquinacridone) Example 27 was repeated except that the mixture with was added. This product (42.4 g) showed an X-ray diffraction pattern of alpha phase 2,9-dichloroquinacridone (FIG. 17). Love out indicated that it was yellowish magenta and more transparent than the product of Example 27.

2 is an X-ray diffraction pattern of the product of Example 1. 2 is an X-ray diffraction pattern of the product of Example 2. 2 is an X-ray diffraction pattern of the product of Example 3. 2 is an X-ray diffraction pattern of the product of Example 4. 7 is an X-ray diffraction pattern of the product of Example 5. 7 is an X-ray diffraction pattern of the product of Example 6. 7 is an X-ray diffraction pattern of the product of Example 7. 9 is an X-ray diffraction pattern of the product of Example 8. 10 is an X-ray diffraction pattern of the product of Example 9. 2 is an X-ray diffraction pattern of the product of Example 10. 2 is an X-ray diffraction pattern of the product of Example 11. 2 is an X-ray diffraction pattern of the product of Example 12. 2 is an X-ray diffraction pattern of the product of Example 13. 2 is an X-ray diffraction pattern of the product of Example 27. 2 is an X-ray diffraction pattern of the product of Example 28. 2 is an X-ray diffraction pattern of the product of Example 29. 2 is an X-ray diffraction pattern of the product of Example 30.

Claims (10)

Formula (B):

A process for producing a quinacridone pigment or a solid solution thereof,
Corresponding formula (A):

[Wherein X and Y are independently one or two substituents selected from the group consisting of H, F, Cl, C ₁ -C ₄ alkyl and C ₁ -C ₄ alkoxy] Or a salt of a mixture of two or more of the 6,13-dihydroquinacridone of formula (A), which is free of pigment residues and oxidants, It is characterized by oxidation in the presence of an aromatic hydroxyl group-containing compound ,
The (hetero) aromatic hydroxyl group-containing compound has the formula (I):

[Where:
k is 1 or 2; and
when k = 1, G is hydrogen or —OR ₂₅ ;
E ₁ and E ₂ are independently of each other the formula ( Ia ) or ( Ib ):

Where
R ₂₅ is hydrogen; C ₁ -C ₁₈ alkyl; OH, halogen, —COOH, —COOR ₂₉ , —CONH ₂ , —CONHR ₃₀ , —CON (R ₃₀ ) (R ₃₁ ), —NH ₂ , NHR ₃₀ , By —N (R ₃₀ ) (R ₃₁ ), —NHCOR ₃₂ , —CN, COR ₃₂ , —OCOR ₃₂ , phenoxy and / or C ₁ -C ₁₈ alkyl-, C ₁ -C ₁₈ alkoxy- or halo-substituted phenoxy -O- are interrupted, and C ₃ -C ₅₀ substituted by OH alkyl;; C ₃ -C ₆ alkenyl; C ₁ -C ₁₈ alkyl which is replacement glycidyl; C ₅ -C ₁₂ Cycloalkyl; C ₅ -C ₁₂ cycloalkyl substituted by OH, C ₁ -C ₄ alkyl or —OCOR ₃₂ ; unsubstituted or OH, Cl, C ₁ -C ₁₈ alkoxy or C ₁ -C ₁₈ alkyl It is substituted C ₇ -C ₁₁ phenylalkyl; -COR ₃₂ or -SO ₂ -R _33; or the formula:

One of the radicals; where
T is hydrogen; C ₁ -C ₈ alkyl; C ₂ -C ₈ alkyl substituted by one or more hydroxyl groups or one or more acyloxy groups; oxyl; hydroxy; -CH ₂ CN; C ₁ -C ₁₈ alkoxy; C ₅ -C ₁₂ cycloalkoxy; C ₃ -C ₆ alkenyl; C ₇ -C ₉ phenylalkyl; once by C ₁ -C ₄ alkyl phenyl ring, C ₇ substituted two or three times It is or aliphatic C ₁ -C ₈ alkanoyl; -C ₉ phenylalkyl;
R ₂₄ is hydrogen; C ₁ -C ₂₄ alkyl or C ₅ -C ₁₂ cycloalkyl; or 1 to 9 halogen atoms, OH, OR ₂₅ , halogen, —COOH, —COOR ₂₉ , —CONH ₂ , —CONHR ₃₀ , —CON (R ₃₀ ) (R ₃₁ ), —NH ₂ , NHR ₃₀ , —N (R ₃₀ ) (R ₃₁ ), —NHCOR ₃₂ , COR ₃₂ , —OCOR ₃₂ , —CN, —NO ₂ , — SR ₃₂ , —SOR ₃₂ , —SO ₂ R ₃₂ , —P (O) (OR ₂₅ ) ₂ , morpholinyl, piperidinyl, 2,2,6,6-tetramethylpiperidinyl, piperazinyl or N-methylpiperazinyl C ₁ -C ₂₄ alkyl or C ₅ -C ₁₂ cycloalkyl substituted by a group or a combination thereof; or 1-6 phenylene, —O—, —NR ₂₉ —, —CONR ₂₉ —, —COO -, -OCO-,- _{H (R 33) -, -} C (R 33) 2 - or -CO- groups or combinations thereof are interrupted, or a C ₅ -C ₁₂ cycloalkyl or C ₁ -C ₂₄ alkyl; or
R ₂₄ is C ₂ -C ₂₄ alkenyl; halogen; —SR ₃₂ , SOR ₃₂ ; SO ₂ R ₃₂ ; —SO ₃ H; or SO ₃ M;
R ₂₆ , R ₂₇ and R ₂₈ are each independently H, C ₁ -C ₁₂ alkyl; C ₂ -C ₆ alkenyl; C ₁ -C ₁₈ alkoxy; C ₅ -C ₁₂ cycloalkoxy; C ₂ -C ₁₈ alkenoxy; halogen; -C≡N; C ₁ -C ₄ haloalkyl; C ₇ -C _{11 phenylalkyl; COOR 29; CONH 2; -CONHR} 30; -CON (R 30) (R 31); sulfo; C ₂ -C ₁₈ acylamino; OCOR _32; phenyloxy; or C ₁ -C ₁₈ alkyl, phenyloxy which is substituted by C ₁ -C ₁₈ alkoxy or halogen;
R ₂₉ is C ₁ -C ₁₈ alkyl; C ₃ -C ₁₈ alkenyl; C ₃ -C ₅₀ alkyl interrupted by O, NH, NR ₃₀ or S and / or substituted by OH ; glycidyl; C ₅ -C ₁₂ cycloalkyl; C ₁ -C ₄ alkyl cyclohexyl; phenyl; C ₇ -C ₁₄ alkylphenyl; C ₆ -C ₁₅ bicycloalkyl; C ₆ -C ₁₅ bicycloalkenyl; C ₆ -C ₁₅ tricycloalkyl; C ₆ -C ₁₅ bicycloalkylalkyl; or C ₇ -C ₁₁ phenylalkyl;
R ₃₀ and R ₃₁ are, independently of one another, C ₁ -C ₁₂ alkyl; C ₃ -C ₁₂ alkoxyalkyl; C ₂ -C ₁₈ alkanoyl; C ₄ -C ₁₆ dialkylaminoalkyl or C ₅ -C ₁₂ cycloalkyl. Or
R ₃₀ and R ₃₁ together are C ₃ -C ₉ alkylene or -oxaalkylene or -azaalkylene;
R ₃₂ is C ₁ -C ₁₈ alkyl; C ₁ -C ₁₂ alkoxy; C ₂ -C ₁₈ alkenyl; C ₇ -C ₁₁ phenylalkyl; C ₇ -C ₁₁ phenylalkoxy; C ₆ -C ₁₂ cycloalkyl; ₆ -C _{1 2} cycloalkoxy; or a phenoxy or phenyl; or -O- are interrupted, and be a good C ₃ -C ₅₀ alkyl optionally substituted by OH;
R ₃₃ is C ₁ -C ₁₈ alkyl; C ₂ -C ₁₈ alkenyl; C ₆ -C ₁₂ cycloalkyl;
At least one G is an —OR ₂₅ group;
When k = 2
E ₁ and E ₂ are groups of formula ( Ia );
G is C ₂ -C ₁₆ alkylene, C ₄ -C ₁₂ alkenylene, xylylene, C ₃ -C ₂₀ alkylene interrupted by O and / or substituted by OH , or the formula: —CH ₂ CH (OH _{) CH 2 O-R 34 -OCH} 2 CH (OH) CH 2 -, - CO-R 35 -CO -, - CO-NH-R 36 -NH-CO -, - (CH 2) j -COO-G ₂₀ —OOC— (CH ₂ ) _j — (where j is a number in the range of 1 to 3) or the following formula:

Indicated by;
R ₃₄ is C ₂ -C ₁₀ alkylene; O, phenylene, or C ₄ -C ₅₀ alkylene interrupted by the group: -phenylene-E-phenylene- , where E is -O-, -S _{-, - SO 2 -, -} CH 2 -, - CO-, or -C (CH _{3) 2} - a is);
R ₃₅ is C ₂ -C ₁₀ alkylene, C ₂ -C ₁₀ oxaalkylene, C ₂ -C ₁₀ thiaalkylene, C ₆ -C ₁₂ arylene or C ₂ -C ₆ alkenylene;
R ₃₆ represents C ₂ -C ₁₀ alkylene, phenylene, tolylene, diphenylene methane or the following formula:

A group represented by:
M is an alkali metal]
A process wherein the (hetero) aromatic hydroxyl group-containing compound is used in an amount of 1 to 25% by weight relative to the weight of dihydroquinacridone . The (hetero) aromatic compound has the formula (I):

[Where:
G is hydrogen or —OR ₂₅ ;
k is 1,
E ₁ and E ₂ are, independently of one another, formula (Ia) or (Ib):

In a group represented, wherein R ₂₅ is hydrogen; C ₁ -C ₁₈ alkyl; OH, it is a C ₁ -C ₁₈ alkyl which is substituted by -COOR _29;
R ₂₄ is hydrogen; C ₁ -C ₂₄ alkyl or C ₅ -C ₁₂ cycloalkyl;
R ₂₆ , R ₂₇ and R ₂₈ are, independently of one another, hydrogen, C ₁ -C ₁₂ alkyl or C ₁ -C ₁₈ alkoxy;
The method of claim 1 , wherein R ₂₉ is C ₁ -C ₁₈ alkyl; provided that at least one G is an OR ₂₅ group. Formula (B):

A process for producing a quinacridone pigment or a solid solution thereof,
Corresponding formula (A):

[Wherein X and Y are independently one or two substituents selected from the group consisting of H, F, Cl, C ₁ -C ₄ alkyl and C ₁ -C ₄ alkoxy] Or a salt of a mixture of two or more of the 6,13-dihydroquinacridone of formula (A), which is free of pigment residues and oxidants, It is characterized by oxidation in the presence of an aromatic hydroxyl group-containing compound,
(Hetero) aromatic hydroxyl group-containing compounds have the formulas ( II ) to ( III ) :

_{Wherein, R 37, R 38, R} 39 and R _40, independently of one another, hydrogen, OH, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, Cl, Br, F, COOH ; COOR 29 CN; CON (R ₃₀ ) ₂ ; N (R ₃₀ ) ₂ (wherein R ₂₉ and R ₃₀ are as defined in claim 1 ); and NO ₂ ],
A process wherein the (hetero) aromatic hydroxyl group-containing compound is used in an amount of 1 to 25% by weight relative to the weight of dihydroquinacridone . R _37, R _38, R ₃₉ and R ₄₀ are, independently of one another, hydrogen, OH, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, Cl, Br, F or COOH, according to claim 3, wherein the method of. The method according to claim 3 , wherein the (hetero) aromatic hydroxyl group-containing compound is selected from the group consisting of resorcinol, hydroquinone, naphthol, catechol, phloroglucinol, dihydroxybenzoic acid, pyrogallol and dihydroxy-2-naphthoic acid. a) Formula (B):

[Wherein X and Y are independently one or two substituents selected from the group consisting of H, F, Cl, C ₁ -C ₄ alkyl and C ₁ -C ₄ alkoxy] Quinacridone, represented by
b) A composition comprising an effective amount of a (hetero) aromatic hydroxyl group-containing compound of formula (I) according to claim 1 . A composition comprising a high molecular weight organic material and an effective coloring amount of the composition of claim 6 . A method for coloring a high molecular weight organic material, comprising kneading an effective coloring amount of the composition of claim 6 into the high molecular weight organic material. a) Formula (A):

Wherein, X and Y are, independently of each other, hydrogen, halogen, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy] quinacridone represented by, and b) an effective amount of claim 1, wherein A composition comprising a (hetero) aromatic hydroxyl group-containing compound of formula (I) or formula ( II ) to ( III ) of claim 3 . Use of a (hetero) aromatic hydroxyl group-containing compound of formula (I) according to claim 1 or of formulas ( II ) to ( III ) according to claim 3 as phase director and / or particle size reducing agent.

Images